B.Sc (HONORS) DEGREE IN CHEMISTRY

FIRST SEMESTER

THEORY

CHA HCT: 1.1. FUNDAMENTALS OF CHEMICAL ANALYSIS

UNIT-I

Analytical chemistry-meaning and analytical prospective, scope and function: Analytical problems and their solutions, trends in analytical methods and procedures.

Language of analytical chemistry - analysis, determination and measurement. Techniques, methods, procedures and protocols. Classifying analytical techniques. Selecting an analytical method-accuracy, precision, sensitivity, selectivity, robustness and ruggedness. Scale of operation, equipment, time and cost. Making the final choice.

Errors and treatment of analytical data:Limitations of analytical methods-Error-determinate and indeterminate errors, minimization of errors. Accuracy and precision. Distribution of random errors, the normal error curve. Statistical treatment of finite samples-measures of central tendency and variability-mean, median, range, standard deviation and variance. Student’s t-test. Confidence interval of mean. Testing for significance-comparison of two means and two standard deviations. Comparison of an experimental mean and a true mean. Criteria for the rejection of an observation-Q-test. Propagation of errors-determinate errors and indeterminate errors.

Standardization and calibration: Comparison with standards-direct comparison and titrations. External standard calibration-the least squares method, regression equation, regression coefficient. Internal standard methods and standard-addition methods. Figures of merit of analytical methods-sensitivity and detection limit, linear dynamic range.

[16 HOURS]

UNIT-II

Obtaining and preparing samples for analysis: Importance of sampling, designing a sample plan-random, judgement, systematic-judgement, stratified and convenience sampling. Type of sample to collect-grab and composite samples. Insitu sampling. Size of sample and number of samples. Implementing the sampling plan-solutions, gases and solids. Bringing solid samples into solution-digestion and decomposing.

Titrimetric analysis:An overview of titrimetry. Principles of titrimetric analysis. Titration curves. Titrations based on acid-base reactions-titration curves for strong acid - strong base, weak acid – strong base and weak base – strong acid titrations. Selecting and evaluating the end point. Finding the end point with visual indicators, end point by monitoring pH and temperature. Quantitative applications – selecting and standardizing a titrant, inorganic analysis-alkalinity, acidity and free CO2 in water and waste waters, nitrogen, sulphur, ammonium salts, nitrates and nitrites, carbonates and bicarbonates. Organic analysis-functional groups like carboxylic acid, sulphonic acid, amine, ester, hydroxyl and carbonyl. Air pollutants like SO2. Quantitative calculations. Characterization applications-equivalent weights and equilibrium constants.

Acid-base titrations in non-aqueous media: Role of solvent in acid-base titrations, solvent systems, differentiating ability of a solvent, some selected solvents, titrants and standards, titration curves, effect of water, determining the equivalence point, typical applications-determination of carboxylic acids, phenols and amines.

[16 HOURS]

REFERENCES

  1. Fundamental of Analytical Chemistry, D.A. Skoog, D.M. West, Holler and Crouch 8th edition, 2005, Saunders College Publishing, New York.
  2. Analytical Chemistry, G.D. Christian, 5th ed., 2001 John Wiley & Sons, Inc, India.
  3. Quantitative Analysis, R.A. Day and A.L. Underwood, 6th edition,1993 prentice Hall, Inc. New Delhi.
  4. Vogel’s Textbook of Quantitative Chemical Analysis, J. Mendham, R.C. Denney, J.D.Barnes and M.J.K. Thomas, 6th edition, Third Indian Reprint.2003 Pearson Education Pvt. Ltd., New Delhi.
  5. Analytical Chemistry Principles, John H. Kennedy, 2nd edition, SaundersCollege

Publishing, California, 1990.

  1. Principles and Practicals of Analytical Chemistry, F. W. Fifield and Kealey,

3rd edition, 2000, Blackwell Sci., Ltd. Malden, USA.

  1. Modern Analytical Chemistry, David Harvey, McGraw Hill, New Delhi, 2000.

CHI HCT:1.2. CONCEPTS AND MODELS OF INORGANIC CHEMISTRY UNIT I

Structures and energetics of ionic crystals: Introduction, MX (NaCl, CsCl, ZnS) and MX2( fluorite, rutile, β-crystobalite and cadmium iodide ) types. The perovskite and spinel structures. Thermodynamics of ionic crystal formation. Lattice energy, Born-Haber cycle, Born-Lande equation. Applications of lattice energetics. Ionic radii, factors, affecting the ionic radii, radius ratio rules.

Structures and energetics of inorganic molecules: Introduction, Energetics of hybridization. VSEPR model for explaining structure of AB, AB2E, AB3E, AB2E2, ABE3, AB2E3, AB4E2, AB5E and AB6, molecules. M.O. treatment of homonuclear and heteronuclear diatomic modecules. M.O. treatement involving delocalized π-bonding (CO32- , NO3- , NO2-, CO2 and N3- ), M.O. correlation diagrams (Walsh) for triatomic molecules.

[16 Hours]

UNIT-II

Electron deficient compounds: Diborane and its reactions, higher boranes, ployhedral boranes (preparations, properties, structure and bonding). Wade’s rules, carboranes and metallocarboranes.

Lanthanides: Review of important properties (spectral, magnetic etc). Abundance and extraction, General principles- conventional, solvent extraction and ion exchange methods. Separation from monazite. Chemistry of principal oxidation states (II, III and IV) Uses: lanthanides as shift reagents, high temperature super conductors.

Actinides: Occurrence and preparation of elements, Isolation of the elements: thorium and uranium, enrichment of uranium for nuclear fuel, uranium hydrides, oxides and chlorides. Chemical reactivity and trend. Chemistry of trans-uranium elements.

[16 HOURS]

References:

  1. Basic Inorganic Chemistry – 3rd edn. F.A. Cotton, G. Wilkinson and P.L. Gaus, John Wiley and Sons (2002).
  2. Inorganic Chemistry, 3rd edn. James E. Huheey, Harper and Row Publishers (1983).
  3. Inorganic Chemistry, 3rd edn. G.L. Miessler and D.A. Tarr, Pearson Education (2004).
  4. Inorganic Chemistry, 2nd edn. D.F. Shriver, P.W. Atkins and C.H. Langford, OxfordUniversity Press (1994).
  5. Inorganic Chemistry, 2nd edn. C.E. Housecroft and A.G. Sharpe, Pearson Education Ltd. (2005).
  6. Introduction to Modern Inorganic Chemistry, K.M. Mackay and R.A. Mackay, Blackie Publication (1989).
  7. Concepts and Models of Inorganic Chemistry 3rd edn. B.E. Douglas, D.H. McDaniel and Alexander, Wiley (2001).

CHO HCT: 1.3.STEREOCHEMISTRY AND REACTION MECHANISMS-I

UNIT-I

Stereoisomerism: Projection formulae [Fly wedge, Fischer, Newman and Saw hourse], enantiomers, diasteroisomers, racemic mixture and their resolution, configurational notations of simple moleculesx, DL and RS configurational notations.

Stereoselectivity: Sterioselective reactions, diasteroselective reactions, stereospecific reactions, regioselective & regiospecific reactions.

Opotical Isomerism: Conditions for optical isomerism, optical isomerism due to chiral centres and molecular dissymmetry, allenes and biphenyls, criteria for optical purity.

Geometrical isomerism: Due to C=C, C=N and N=N bonds, E,Z conventions, determination of fonfiguration by physical and chemical methods.

Conformational Isomerism: Elementary account of conformational equillibria of ethane, butane and cyclohexane.

Conformational analysis: Conformation of cyclic compounds such as cyclopentane, cyclohexane, cyclohexanone derivatives and decalins. Conformational analysis of 1,2-; 1,3-, 1,4-disubstituted cyclohexane derivatives and D-Glucose, Effect of conformation on the course of rate of reactions.

[16 hours]

UNIT-II

Structure and reactivity: Acids and Bases, Structural effect on acidity and basicity, hydrogen bonding Resonance, inductive and hyperconjugation effects.

Reaction Intermediates: Formation, structure, stability, detection and reactions of carbocations (classical and non-classical), carbanions, free radicals, carbenes, nitrenes, nitrile oxides, nitrile imines, nitrile ylides and arynes.

Substitution reactions: Mechanism of nucleophilic substitution reactions-Kinetics, Mechanism and stereochemical factor affecting the rate of SN1, SN2, SRN1, SN1, SN2, SNII reactions, Neighbouring group participation.

Aromatic nucleophilic substitution: SN1, SN2 and benzyne mechanism, Bucherer reaction.

Aromatic electrophilic substitution: Mechanism of nitration, halogenation, sulphonation, Friedel-Crafts alkylation and acylation, Mannich reaction, chloromethylation, Vilsmeier-Haack reaction.

[16 hours]

REFERENCES

  1. E. L. Eliel and S. H. Wilen, Stereochemistry of Organic Compounds, Jhon Willey and Sons, New York. 1994.
  2. H. Pine, Hendrickson, Cram and Hammond, Organic Chemistry, Mac Grow Hill, New York, 1987.
  3. Organic Chemistry-Morrison & Boyd
  4. Finar, Organic Chemistry, ELBS Longmann, Vol. I & II 1984.
  5. Basic Principles of Organic Chemistry-Robert & Casereo
  6. N. S. Issacs, Reactive intermediates in Organic Chemistry, Jhon Willey and Sons, New York. 1974.
  7. R. K. Bansal, Organic Reaction Mechanism, Wiley Eastern Limited, New Delhi, 1993.
  8. J. Marcdh, Advanced Organic chemistry, Willey Interscience, 194.
  9. E. S. Gould, Mechanism and structure in Organic Chemistry, Halt, RinhartWinston, New York, 964.
  10. A Guide book to mechanism in Organic Chemistry-Petersyke
  11. F. A. Carey and Sundberg, Advanced Organic Chemistry-Part A & B, 3rd edition, Plenum Press, New York, 1990.

12. P. S. Kalsi, Stereo Chemistry of Organic compounds and solved problems.

CHP HCT: 1.4Chemical Thermodynamics AND CHEMICAL KINETICS

Unit I

Concepts of entropy and free energy: Entropy as a measure of unavailable energy. Entropy change during spontaneous process. Helmholtz and Gibbs free energies. Thermodynamic criteria of equilibrium and spontaneity. Variation of free energy with temperature and pressure.Third law of thermodynamics-calculation of absolute entropies.

Partial molar properties: Partial molar volumes and their determination by intercept method and from density measurements. Chemical potential and its significance. Variation of chemical potential with temperature and pressure. Formulation of the Gibbs Duhem equation. Derivation of Duhem-Margules equation.

Fugacity: Determination of fugacity of gases. Variation of fugacity with temperature and pressure.Activity and activity coefficients. Variation of activity with temperature and pressure. Determination of activity coefficients by vapour pressure, depression in freezing point, solubility measurements and by electrical methods.

Thermodynamics of dilute solutions: Raoult’s law, Henry’s law. Ideal and non-ideal solutions.

[16 hOURS]

Unit II

Kinetics of complex reactions: Parallel, consecutive and reversible reactions. Determination of order of reaction. Arrhenius equation, energy of activation and its experimental determination. Simple collision theory-mechanism of bimolecular reaction. Lindemann’s theory, Hinshelwood’s theory for unimolecular reaction (No derivation). Activated complex theory of reaction rate, classical thermodynamic treatment,

partition function, statistical thermodynamic treatment. Kinetics of reactions in solution-Salt effects, effect of dielectric constant (single sphere and double sphere model), effect of pressure, volume and entropy change on reaction rates. Cage effect with an example. Kinetics of heterogeneous reactions - Langmuir’s theory, unimolecular and bimolecular surface reactions.

Fast Reactions: Study of kinetics by flow techniques, equation for contact time, stopped flow and continuous flow methods. Relaxation method, equation for relaxation time, temperature jump and pressure jump methods, flash photolysis, pulse radiolysis and shock tube method. Potential energy surface, theoretical calculation of energy of activation.

[16 hOURS]

References

  1. Thermodynamics for Chemists by S. Glasstone, Affiliated East-west press, New Delhi, (1965).
  2. Chemical Thermodynamics by I.M. Klotz, W.A. Benzamin Inc. New York, Amsterdam (1964).
  3. Basic Physical Chemistry by W.J. Moore, Prentice Hall of India Pvt. Ltd., New Delhi (1986).
  4. Text book of Physical Chemistry by Samuel Glasstone, MacMillan Indian Ltd., 2nd edition (1974).
  5. Theoretical Chemistry by S. Glasstone.
  6. Elementary statistical thermodynamics by N.D. Smith Plenum Press, NY (1982).
  7. Elements of Physical Chemistry –Lewis and Glasstone.
  8. Physical Chemistry by P.W. Atkins, ELBS, 4th Edition, OxfordUniversity Press

(1990)

  1. Chemical Kinetics by K.J. Laidler.
  2. Chemical Kinetics –Frost and Pearson.
  3. Kinetics and Mechanism of Chemical Transformation by J. Rajaram and J.C. Kuriacose.
  4. Chemical Kinetics –L.K. Jain.
  5. Chemical Kinetics –Benson.
  6. Kinetics in Analytical Chemistry – H. B. Mark and G. A. rechnitz, Interscience

Publishers, John Willey and Sons, New York.

PRACTICALS

CHA HCP: 1.5. ANALYTICAL PRACTICALS-I

  1. Determination of total acidity of vinegar and wines by acid-base titration.
  2. Determination of purity of a commercial boric acid sample, and of Na2CO3 content of washing soda.
  3. Titration of chromate-dichromate mixtures by acid-base titration.
  4. Determination of replaceable hydrogen and relative molecular mass of a weak organic acidby titration with NaOH.
  5. Determination of ephedrine and aspirin in their tablet preparations by residual acid-base titrimetry.
  6. Analysis of urine for sugar using Benedict’s reagent and blood for bicarbonate by acid-base titration.
  7. Titrimetric analysis of a soil sample for calcium carbonate and organic carbon.
  8. Determination of aniline by non-aqueous acid-base titration.
  9. Non-aqueous titrimetric assay of chlorpromazine tablets, injections and elixir/syrup.
  10. Periodate determination of ethylene glycol and glycerol (Malprade reaction).
  11. Determination of carbonate and bicarbonate in a mixture by pH-metric titration andcomparison with visual acid-base titration.
  12. Analysis of water/waste water for acidity by visual and pH metric-titrations.
  13. Analysis of water/waste water for alkalinity by visual and pH metric-titrations.
  14. Determination of carbonate and hydroxide-analysis of a commercial washing soda by visual and pH-titrimetry.
  15. Determination of ammonia in house-hold cleaners by visual and conductometric titration.
  16. Acid rain analysis by standard-addition titration.
  17. Determination of protein in bread by Kjeldahl method.
  18. Potentiometric determination of the equivalent weight and Ka for a pure unknown

weak acid.

19. Spectrophotometric determination of creatinine in urine.

20. Flame emission spectrometric determination of sodium and potassium in

river/lake water.

[64 HOURS]

REFERENCES

1. Fundamental of Analytical Chemistry, D.A. Skoog, D.M. West, Holler and

Crouch 8th edition, 2005, Saunders College Publishing, New York.

2. Analytical Chemistry, G.D. Christian, 5th ed., 2001 John Wiley & Sons, Inc,India.

3. Quantitative Analysis, R.A. Day and A.L. Underwood, 6th edition, 1993

Prentice Hall, Inc. New Delhi.

4. Vogel’s Textbook of Quantitative Chemical Analysis, J. Mendham, R.C. Denney, J.D.

Barnes and M.J.K. Thomas, 6th edition, Third Indian Reprint.2003 PearsonEducation

Pvt. Ltd., New Delhi.

7. Analytical Chemistry Principles, John H. Kennedy, 2nd edition, SaundersCollege

Publishing, California, 1990.

8. Practical Clinical biochemistry methods and interpretations, R.Chawla, J.P. Bothers

MedicalPublishers (P) ltd., 1995.

9. Laboratory manual in biochemistry, J. Jayaraman, New Age International Publishers,

NewDelhi, 1981.

10. Practical clinical Biochemistry-Harold Varley and Arnold.Hein mann, 4th edn.

CHI HCP: 1.6 INORGANIC PRACTICALS-I

  1. Determination of iron in haematite using cerium(IV) solution (0.02M) as the titrant, and gravimetric estimation of insoluble residue.
  2. Estimation of calcium and magnesium carbonates in dolomite using EDTA titration, and gravimetric analysis of insoluble residue.
  3. Determination of manganese dioxide in pyrolusite using permanganate titration.
  4. Qunatitative analysis of copper-nickel in alloy/mixture:
  1. Copper volumetrically using KIO3.
  2. Nickel gravimetrically using DMG
  1. Determination of lead and tin in a mixture: analysis of solder using EDTA titration.
  2. Complexometric determination of calcium and lead in a mixture.
  3. Quantitative analysis of chloride and iodide in a mixture:
  1. Iodide volumetrically using KIO3
  2. Total halide gravimetrically.
  1. Determination of chlorate in commercial samples by iodometric method.
  2. Determination of borax by neutralization titration.
  3. Gravimetric analysis of molybdenum with 8- hydroxyqunoline.
  4. Spectrophotometric determinations of :
  1. Titanium using hydrogen peroxide.
  2. Vanadium using eriochrome cyanine R in micellar medium.
  3. Chromium using diphenyl carbazide in industrial effluents.
  4. Iron using thiocyanate/1,10-phenanthroline method in commercial samples.
  5. Nickel using dimethylglyoxime in steel solution.
  1. Circular paper chromatographic separation of (Demonstration):
  1. Iron and nickel
  2. Copper and nickel

[64 HOURS]

REFERENCES

  1. A Text Book of Quantitative Inorganic Analysis – A.I. Vogel, 3rd edition.
  2. Vogel’s Text Book of Quantitative Chemical Analysis – 5th edn, J. Basset, R.C. Denney, G.H. Jeffery and J. Mendhom.
  3. Spectrophotometric determination of elements – Z. Marczenko.
  4. Quantitative Chemical Analysis – Daniel C. Harris, 7th edition, (2006)

CHO SCP1:1.7. ORGANIC PRACTICALS - IA

  1. Preparation of parabromoaniline from acetanilide.
  2. Preparation of n-butyl bromide from n-butanol.
  3. Preparation of p-nitroiodobenzene from paranitroaniline.
  4. Preparation of aniline from nitrobenzene.
  5. Preparation of ß-D-Glucose penta acetate.
  6. Preparation of phenoxy acetic acid.
  7. Preparation of cyclohexanol to cyclohexanone.
  8. Preparation of chalcone.
  9. Preparation of S-Benzylthiuronium chloride.
  10. Condensation of anthracene and maleic anhydride (Diels-Alder reaction).
  11. Preparation of m-nitrobewnzoic acid from methyl benzoate.

[64 HOURS]

CHO SCP2:1.7 ORGANIC PRACTICALS - IB

1. Preparation of p-nitro aniline from acetanilide.

2. preparation of Glucosazone.

3. Preparation of cis and trans cinnamic acid.

4. Preparation of paraamino azobenzene.

5. Preparation of Benzoic acid (cannizaro’s reaction).

6. Preparation of anthroquinone.

7. Preparation of 4-methyl-7-hydroxy coumarin (pechmann reaction)

8. Preparation of paratoluidine from paranitrotoluene.

9. Preparation of cinnamic acid.

10. Preparation of benzophenone

[64 HOURS]

REFERENCES

  1. A Text book of practical organic Chemistry – A. I. Vogel Vol.I
  2. Practical Organic Chemistry-Mann & Saunders.
  3. Manual of Organic Chemistry –Dey and Seetharaman.
  4. An introduction to practical organic Chemistry-Robert, Wingrove etc.
  5. Semimicro qualitative organic Analysis by Cheronis, Entrikin and Hodnet.
  6. J. N. Guthru & R. Kapoor, Advance experimental Chemistry, S. Chand Company, New Delhi-1991.
  7. R. K. Bansal, Laboratory Manual of Organic Chemistry, New PGE International (P) LTd. London, 3rd edition. 1996.
  8. N. K. Visno, Practical Organic Chemistry, New PGE International (P) Ltd. London, 3rd edition, 1996.

CHP SCP1:1.8 PHYSICAL PRACTICALS -IA

  1. Study of kinetics of hydrolysis of an ester using HCl/H2SO4 at two different temperatures, determination of rate constants and energy of activation.
  2. Study of kinetics of reaction between K2S2O8 and KI, first order, determination of rate constants at two different temperatures and Ea.
  3. Conductometric titration of a mixture of HCl and CH3COOH against NaOH.
  4. Conductometric titration of a mixture of HCl, CH3COOH and CuSO4 against NaOH.
  5. Potentiometric titration of KI vs KMnO4 solution.
  6. Determination of dissociation constant of a weak acid by potentiometric method.
  7. Potentiometric titration of AgNO3 vs KCl.
  8. To obtain the absorption spectra of coloured complexes, verification of Beer’s law and estimation of metal ions in solution using a spectrophotometer.
  9. Spectrophotometric titration of FeSO4 against KMnO4.
  10. Determination of heat of solution of benzoic acid by variable temperature method (graphical method).
  11. Thermometric titration of hydrochloric acid with a NaOH.
  12. Determination of molecular weight of a compound using Bekmann’s cryoscopic method using benzene or/and water as solvent.
  13. Potentiometric titrations of (a) Fe(II) vs V(V).
  14. Kinetics of photodegradation of indigocarmine (IC) using TiO2 as photocatalyst and study the effect of [TiO2] and [IC] on the rate of photo degradation.
  15. Conductometry –To determine the degree of hydrolysis and hydrolysis constant of aniline hydrochloride.
  16. Conductometric titration of potassium iodide with mercuric perchlorate.
  17. Determination of the molecular weight of a polymer material by viscosity measurements (cellulose acetate/methyl acrylate).

[64 HOURS]

CHP SCP2:1.8 PHYSICALPRACTICALS -IB

  1. Study of kinetics of hydrolysis of an ester using HCl/H2SO4 at two different concentrations, determination of rate constants and compare the rate constants.
  2. Study of kinetics of reaction between K2S2O8 and KI, second order, determination of rate constant and Ea.
  3. Conductometric titration of a mixture of HCl and ClCH2COOH against NaOH.
  4. Conductometric titration of a mixture of HCl, HCOOH and CuSO4 against NaOH.
  5. Potentiometric titration of KCl vs KMnO4 solution.
  6. Determination of dissociation constant of acetic acid by potentiometric method.
  7. Potentiometric titration of AgNO3 vs. KBr.
  8. Verification of Beer’s law and calculation of molar extinction coefficient for CuSO4 system.
  9. Spectrophotometric titration of FeSO4 against K2Cr2O7.
  10. Determination of heat of solution of salicylic acid by variable temperature method (Graphical method).
  11. Thermometric titration of sulphuric acid with a NaOH.
  12. Potentiometric titrations of (a) Fe(II) vs. Ce(IV).
  13. Kinetics of photodegradation of indigocarmine (IC) using ZnOas photocatalyst and study the effect of [ZnO] and [IC] on the rate of photo degradation.
  14. Conductometry –To determine the degree of hydrolysis and hydrolysis constant of aniline hydrochloride.
  15. Conductometric titration of potassium iodide with mercuric perchlorate.
  16. Determination of the molecular weight of a polymer material by viscosity measurements (polyvinyl alcohol/polystyrene).

[64 HOURS]